Guoqiang Shan

Photolytic reaction mechanism and impacts of coexisting substances on photodegradation of bisphenol A by Bi2WO6 in water

Bi(2)WO(6) displayed great photolytic degradation efficiency to bisphenol A (BPA) under simulated solar light irradiation but its reaction mechanism and the impacts of coexisting substances on the degradation remain unclear. In present study, the reaction mechanism was investigated using DMPO spin-trapping ESR spectra and experiments with scavengers of hydroxyl radicals (*OH) and holes. The results supported that hole oxidation mainly governed the photodegradation process. As a common humic substance in natural water, humic acid accelerated the degradation of BPA when its concentration was 1mg/L, while the photodegradation was impeded with the increase of humic acid concentration in the range of 5-20mg/L. Almost all anions, including NO(3)(-), HCO(3)(-), Cl(-), SO(4)(2-) inhibited the degradation of BPA by Bi(2)WO(6) and their inhibition effects followed the order of SO(4)(2-)>Cl(-)>HCO(3)(-)>NO(3)(-). Cations of Na(+), K(+), Ca(2+) and Mg(2+) displayed slight suppressing effect on BPA degradation mainly due to the impact of Cl(-) coexisting in the solution. However, Cu(2+) hindered the BPA photodegradation heavily. Fe(3+) and H(2)O(2) affected the photodegradation in a complicated way: they suppressed or promoted the photodegradation depending on their concentrations. This could be the result of competition between photolyitc hole generated by Bi(2)WO(6) and OH produced by Fe(3+) or H(2)O(2.).

Photocatalytic Degradation Efficiency and Mechanism of Microcystin-RR by Mesoporous Bi2WO6 under Near Ultraviolet Light

Microcystin-RR (MC-RR) is one of the most common cyanotoxin microcystins in fresh water and is of great concern due to its potential hepatotoxicity. In the present study, Bi(2)WO(6) was synthesized with a hydrothermal method by varying the pH of the reaction solution in the range of 1-11. The surface area of the catalysts decreased, but the crystallinity and crystal size increased with the pH. The adsorption and degradation capacities of the catalysts decreased with increasing the preparation solution pH. The Bi(2)WO(6) prepared at pH 1 (Bi(2)WO(6)-pH1) displayed the highest adsorption and degradation capacity to MC-RR even though it consisted of randomly aggregated particles. Nearly 100% of MC-RR at 10 mg L(-1) was removed after 30 min of irradiation of near-ultraviolet light (300-400 nm) in a solution with Bi(2)WO(6) concentration of 0.2 g L(-1). The photodegradation efficiency of Bi(2)WO(6)-pH1 was greater in acid medium than in basic solutions. Several intermediate products were observed and identified by liquid chromatography/mass spectrometry/mass spectrometry, and a unique photodegradation pathway was proposed. It was assumed that a photo-Kolbe process happened at the site carboxyl acid group of the d-Glu residue by the photogenerated holes, producing a hydroperoxyl product at m/z 513.8. This intermediate could be further decomposed to an alcohol product at m/z 505.8 and a ketone product at m/z 504.8. The aromatic ring and diene bond of the Adda chain could also be attacked by the holes and form phenol and diol products.

Concentration profiles and spatial distribution of perfluoroalkyl substances in an industrial center with condensed fluorochemical facilities

Jiangsu Hi-tech Fluorochemical Industry Park, China, is one of the largest fluorochemical industry centers in Asia and could be a point source of polyfluoroalkyl substances (PFASs) to the surrounding environment. Besides water, sediment and soil samples, tree leaves and bark were also collected to monitor airborne PFASs around the facilities. Perfluorooctanoic acid and short-chain perfluorocarboxylates including perfluorohexanoic acid and perfluoropentanoic acid were found predominantly in all the samples. The target ∑PFASs were distributed in the dissolved phase with a proportion of 96.5±2.9%. High concentrations of ∑PFASs (up to 12,700 ng/L in surface water) were found at sites near and within the wastewater treatment plant and the facilities. The ∑PFASs in the sediment/sludge were in the range of 3.33-324 ng/g dw. For the first time, tree samples were used for bio-monitoring airborne PFASs in the environment. The ∑PFASs in the tree leaf and bark samples were in the range of 10.0-276 and 6.76-120 ng/g dw, respectively. The spatial distribution of ∑PFASs in the tree leaves suggested that airborne PFASs could be transported from the center to the surrounding environment by prevailing wind.

Highly active magnetic bismuth tungstate/magnetite composite under visible light irradiation in the presence of hydrogen peroxide

Bi2WO6/Fe3O4 composites were synthesized using hydrothermal method and their photocatalytic activity to degrade rhodamine B (RhB) under visible light irradiation assisted with H2O2 and underlying mechanisms were investigated. The composites were 3D flower-like microspheres constructed by 2D Bi2WO6 nanosheets loaded with spherical Fe3O4 nanoparticles. The composited photocatalysts could be easily harvested from the reaction solution by an external magnetic field. In the presence of H2O2, a large amount of hydroxyl radicals (·OHs) were produced by H2O2 reacting with photogenerated electrons. Fe3O4 not only promoted the separation of hole-electron pairs but also acted as a Fenton-like reagent, expediting the production of ·OH. Thus, the composites in the presence of H2O2 displayed much higher photocatalytic efficiency to degrade RhB than pure Bi2WO6. 98% of RhB (initial concentration 10 mg/L) was degraded in 2 h visible irradiation and 60% of total organic carbon (TOC) was removed in 3 h by 0.5 g/L Bi2WO6/Fe3O4 (5:1). The composite displayed high photodegradation efficiency at pH 3-9. Our study suggests that a visible light driven and highly active magnetic photocatalyst-Fenton coupling oxidation system may have potential application in water treatment and environmental cleaning.

Bioaccumulation and biomagnification of emerging bisphenol analogues in aquatic organisms from Taihu Lake, China

Due to regulations on bisphenol A (BPA) in many countries, a variety of bisphenol analogues are being widely manufactured and applied. However, there is a big knowledge gap on bioaccumulation and biomagnification of these emerging bisphenols in aquatic organisms. The bioaccumulation and magnification of nine bisphenol analogues in aquatic organisms at different trophic levels collected from Taihu Lake, China, were evaluated. The total concentrations of the nine bisphenols in the lake waters were in the range of 49.7-3480ng/L (mean, 389ng/L). BPA, bisphenol AF (BPAF) and bisphenol S (BPS) were the most predominant analogues in the water. The mean natural logarithm bioaccumulation factor (log BAFs) of BPAF, bisphenol C (BPC), bisphenol Z (BPZ) and bisphenol E (BPE) were greater than BPA, and there was a significantly positive correlation between log BAFs of the biphenols and their octanol-water partition coefficients (log Kow). The trophic magnification factors of BPAF, BPC and BPZ were 2.52, 2.69 and 1.71, respectively, suggesting that they had the potential to biomagnify in the food web. The results of this study call for further investigations on risk assessment of these emerging pollutants in the environment.

Riverine inputs and source tracing of perfluoroalkyl substances (PFASs) in Taihu Lake, China

The occurrence, riverine inputs and sources of perfluoroalkyl substances (PFASs) in Taihu Lake, one of the largest lakes in China, were investigated by measuring PFASs including the isomers of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) and perfluorohexanesulfonate (PFHxS) in the Lake and its main flow-in rivers. It was found that PFHxS, instead of PFOS or PFOA, was predominant both in the Lake and rivers (45.9-351ng/L), reflecting increasing demand of PFHxS in recent years. The riverine flux of PFASs into the Lake was estimated to be 1255kg/year. The percentage of linear (n-) PFOS and the ratio of 3+5m-/1m-PFOS were combined to indicate indirect source due to biodegradation of PFOS-precursors. The percentage order of n-PFOS was: the Lake (48.7%)the rivers (8.99)>ECF (electrochemical fluorination) product (6.76). These suggested that degradation of PFOS-precursors made distinct contribution to PFOS load in the waters, particularly in the Lake. The Lake and river waters had a consistent proportion of n-PFHxS (89.0%), which was slightly lower than the ECF product (96.0%), indicating it was mainly due to the release from production and application of PFHxS as an active ingredient.

Occurrence, partitioning and bioaccumulation of emerging and legacy per- and polyfluoroalkyl substances in Taihu Lake, China

There are many studies about the occurrence of legacy perfluoroalkyl acids (PFAAs) in fresh water ecosystem, but related information about emerging per- and polyfluoroalkyl substances (PFASs) is limited. In this study, along with ten legacy PFAAs, twelve non-PFAAs, including precursors of perfluorooctane sulfonic acid (PFOS) and emerging PFASs in the water, sediment and organisms in Taihu Lake, China, were investigated. As one replacement product of PFOS, perfluorohexane sulfonic acid (PFHxS) (mean: 69.3ng/L) was the predominant PFAA in the water samples. Perfluorooctanesulfonamide (PFOSA) (mean: 0.190ng/L) and 6:2 fluorotelomer phosphate diester (6:2 diPAP) (0.034ng/L) were detected in all the water samples. Other emerging PFASs, such as N-ethyl perfluorooctanesulfonamidoa-cetic acid (NEtFOSAA), bis(perfluorohexyl) phosphinic acid (6:6 PFPiA) were frequently detected in the sediment and/or organisms. The organic carbon normalized sediment-water distribution coefficients (KOC) and bioaccumulation factors (BAFs) of the PFASs generally increased with their log KOW values. However, PFOSA, NEtFOSAA, 6:2 diPAP and 6:6 PFPiA displayed lower log BAFs, and/or lower log KOC than expected, which may be due to biotransformation potentials and/or large molecular size. PFOSA was not biomagnified in the food web. For other emerging PFASs, the low detection frequencies in the organisms hampered us to evaluate their biomagnification potentials. The lower percentage of most of the branched PFOS isomers while higher percentage of 1m-PFOS in the organisms suggested that there was indirect source of PFOS in the organisms. Similar to PFOS and PFOA, linear PFHxS isomer was preferentially enriched in organisms relative to its branched isomers.